Cathode active material for secondary battery and manufacturing method thereof

ABSTRACT

The present invention relates to a cathode active material for a secondary battery and a manufacturing method thereof. A cathode active material, according to one embodiment of the present invention, comprises silicon-based primary particles, and a particle size distribution of the silicon-based primary particles is D10≥50 nm and D90≤150 nm. The cathode active material suppresses or reduces tensile hoop stress generated in lithiated silicon particles during a charging of a battery to thus suppress a crack due to a volume expansion of the silicon particles and/or an irreversible reaction caused by the crack, such that the lifetime and capacity of the battery can be improved.

FIELD OF THE INVENTION

The present invention relates to secondary battery technology and more particularly, to a cathode active material for a secondary battery and a preparation method thereof.

BACKGROUND TECHNOLOGY

A secondary battery is a lithium secondary battery that can be charged and discharged using an electrode material having excellent reversibility, and one of the most popular commercialized examples is a lithium secondary battery. The lithium secondary battery is expected to be applied as a medium/large-sized power source mounted on transportation means (e.g. automobiles) or used for power storage in a power supply network (e.g. smart grid), and also as a compact power source for small IT devices (e.g. smart phones, portable computers, and electronic paper).

When a lithium metal is used as a negative electrode of a lithium secondary battery, there is a risk that a short-circuit or explosion may occur due to the formation of a dendrite. Therefore, instead of the lithium metal, crystalline carbon (e.g. graphite and artificial graphite) soft carbon, hard carbon, and carbon-based active materials to which lithium can be intercalated and deintercalated, are widely used. However, with the expansion of the application of the secondary battery, there is an increasing demand for higher capacity and higher output of a secondary battery. Accordingly, non-carbon negative electrode materials having a capacity of 500 mAh/g or greater (e.g. silicon (Si), tin (Sn), or aluminum (Al)), which can replace carbon-based negative electrode materials having a theoretical capacity of 372 mAh/g and can be alloyed with lithium, are spotlighted.

Among these non-carbon negative electrode materials, silicon has the largest theoretical capacity, which is about 4,200 mAh/g, and thus the commercialization of silicon is very important in terms of capacity. However, the volume of silicon increases by about four times during charging, and thus the electrical connection between active materials may be destroyed or the active material may be separated from a current collector due to the volume change during charging and discharging, and the progress of an irreversible reaction (e.g. formation of a solid electrolyte interface (SEI) layer (e.g. Li₂O)) due to corrosion of the active material by the electrolyte, and subsequent deterioration in lifetime make the commercialization of silicon difficult. Accordingly, for commercialization of the silicon material, it is required that the capacity and lifetime of a battery be maximized while preventing the changes in volume during charging and discharging.

DETAILED DESCRIPTION OF THE INVENTION Technical Problem

Accordingly, a technical object to be solved in the present invention is to provide a cathode active material for a secondary battery having high capacity and long lifetime while having high energy density, by improving irreversible capacity and suppressing changes in volume according to charging/discharging, by using silicon.

Additionally, another technical object to be solved in the present invention is to provide a method for preparing a cathode active material for a secondary battery having the advantages described above.

Additionally, a further technical object to be solved in the present invention is to provide a lithium battery using the cathode active material for a secondary battery having the advantages described above.

Technical Solution

To achieve the above objects, the cathode active material according to an embodiment of the present invention may include silicon-based primary particles and the particle size distribution of the silicon-based primary particles may be D10≥50 nm and D90≤150 nm.

The silicon-based primary particles may have sphericity in the range of 0.5 to 0.9.

In another embodiment, the cathode active material for a secondary battery may further include a silicon oxide layer formed on the silicon-based primary particles. The oxygen content relative to the total weight of the silicon particle cores and the total weight of the silicon oxide is limited to the range of 9 wt % to 20 wt %. The purity of the silicon-based primary particles may be 99% or greater and the particle distribution width of the silicon-based primary particles may be 1.0 or less.

To achieve another object, the method for preparing a cathode active material according to an embodiment may include: a step of providing silicon powder; a step of providing a dispersion mixture in which the silicon powder is dispersed in an oxidizing solvent; a step of applying mechanical stress energy (Es) to the silicon powder of the dispersion mixture to form refined silicon particles in which the particle size distribution is D10≥50 nm and D90≤150 nm; and a step of drying the resulting product including the refined silicon particles to obtain silicon-based primary particles. The step of forming the refined silicon particles may be a step of forming a chemical oxide layer on the refined silicon particles by means of the oxidizing solvent while simultaneously applying the mechanical stress energy.

The oxidizing solvent may include water, deionized water, an alcoholic solvent, or a mixture of two or more thereof. The alcoholic solvent may include any solvent selected from the group consisting of ethyl alcohol, methyl alcohol, glycerol, propylene glycol, isopropyl alcohol, isobutyl alcohol, polyvinyl alcohol, cyclohexanol, octyl alcohol, decanol, hexadecanol, ethylene glycol, 1,2-octanediol, and 1,2-dodecanediol, and 1,2-hexadecanediol, or a mixture thereof.

The application of mechanical stress energy may be achieved by a mill pulverization process using a composition of abrasive particles along with the oxidizing solvent. The application of mechanical stress energy may be carried out by grinding which performs pressing and abrasion while simultaneously supplying the dispersion mixture between a spinning abrasive plate and a fixed plate. The mechanical stress energy may be defined by the equation below:

${Es} = \frac{\pi*d*V}{60*\eta}$

in which π is a circumferential rate, d is a diameter of a rotor, V is an RPM, and η is a viscosity.

Advantageous Effects of the Invention

According to an embodiment of the present invention, a cathode active material for a secondary battery may be provided, in which an irreversible reaction caused by cracks and/or fractures caused by a volume expansion of silicon-based primary particles is suppressed such that the lifetime and capacity of the battery can be improved, by suppressing or reducing tensile hoop stress generated in lithiated silicon by controlling the particle size distribution of the silicon-based primary particles to be D10≥50 nm and D90≤150 nm.

Additionally, according to yet another embodiment of the present invention, in the preparation of the silicon-based primary particle, a method for preparing a cathode active material for a secondary battery capable of contributing to the improvement of the lifetime of an active material particle may be provided, in which excessive expansion of the core of the silicon particle during charging/discharging and subsequent undifferentiation are prevented and stable formation of a solid electrolyte interface (SEI) is induced, by applying mechanical stress energy in a certain range to refine silicon powder while simultaneously forming the oxide layer (hereinafter, a chemical oxide layer), which was formed on the silicon particles by a wet method using an oxidizing solvent, on the core of the silicon particle or controlling the oxygen content within the silicon particle.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the comparison results of particle size distribution of silicon-based primary particles according to the examples and comparative examples of the present invention.

FIG. 2 is a flowchart showing a method of preparing silicon-based primary particles according to an embodiment of the present invention.

FIG. 3 is a cross-sectional view of an electrode employing silicon-based primary particles according to an embodiment of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, preferred embodiments will be described in detail with reference to accompanying drawings.

Examples of the present invention are provided to more fully describe the present invention to those skilled in the art. The following examples may be modified in various ways, but the scope of the present invention is not limited to these examples described hereinbelow. Rather, these examples are provided so that the present disclosure will be more faithful and complete and fully convey the spirit of the present invention to those skilled in the art.

Additionally, in the drawings, the thickness and size of each layer are exaggerated for convenience and clarity of explanation, and like reference numerals refer to like elements in the drawings. As used herein, the term “and/or” includes any and all combinations of any of the listed items.

The terminology used herein is used for the purpose of describing particular embodiments and is not intended to be limiting of the invention. As used herein, the singular forms may include the plural forms as well, unless the context explicitly indicates otherwise. Additionally, it is apparent that the terms “comprise” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, members, components, and/or groups thereof, but do not exclude the presence or addition of one or more other features, integers, steps, operations, members, components, and/or groups thereof.

The examples according to the present invention relate to the improvement of the capacity and lifetime of a lithium secondary battery, in which silicon particles are used as a cathode active material, by controlling the range of the particle distribution of silicon powder, and to a secondary battery using the same. In general, it is known that the drastic decrease in lifetime and increase in the irreversible capacity in cathodic applications of silicon particles are due to the large volume expansion and contraction of silicon particles during lithiation/delithiation. As such, the present inventors have discovered that when the particle size distribution of the silicon primary particles is prepared so as to be small and uniform within a certain range, it is possible to reduce the phenomenon of the irreversible capacity increasing and the lifetime characteristic deteriorating due to the volume expansion in the cathode active material, and thereby the present inventors have derived the present invention.

According to an embodiment of the present invention, a cathode active material may include silicon-based primary particles, and the silicon-based primary particles may have a particle distribution in the range of D10≥50 nm, D90≤150 nm, in which D100 may be less than 250 nm. In the present invention, D10 may be defined as a size of a particle (or particle size) corresponding to a volume of 10% in a cumulative size-distribution curve with a total volume of 100%; D90 as a size of a particle (or particle size) corresponding to a volume of 90% in the cumulative size-distribution curve; and D100 as a size of a particle (or particle size) corresponding to a volume of 100% in the cumulative size-distribution curve, that is, D100 represents the size of the coarsest particle among the distributed particles. When the silicon-based primary particles are prepared so as to have the above particle size distribution range, it is possible to reduce the phenomenon of the irreversible capacity increasing and the lifetime characteristic deteriorating due to the volume expansion in the cathode active material.

Additionally, according to an embodiment of the present invention, the median particle size of the silicon-based primary particles, D50, represents a particle size corresponding to a volume of 50% in the particle size cumulative distribution curve (or the cumulative average particle diameter), and D50 may be 80 nm to 100 nm. When the D50 of the silicon-based primary particles is less than 80 nm, the relative proportion of the conductive layer or the conductive material in the form of particles in the active material slurry becomes large and thus the battery capacity is lowered, whereas when the D50 of the particles exceeds 100 nm, the capacity retention is lowered due to the increase of the irreversible capacity.

FIG. 1 is a graph comparing the particle size distribution according to the examples and comparative examples of the present invention. For the definitions on Examples 1 to 3 and Comparative Examples 1 and 2 please refer to Tables 1 and 2 shown below.

With reference to FIG. 1, the silicon-based primary particles having a particle size distribution according to the examples of the present invention have a narrower particle distribution width than those of the comparative examples. In general, the particle distribution width may be defined as a value of (D90−D10)/D50. According to an embodiment of the present invention, when the particle distribution width of the silicon-based primary particles is 1 or less, and preferably 0.9 or less, the increase of the irreversible capacity due to the volume expansion can be alleviated within a cathode active material, and consequently the lifetime characteristic of a secondary battery can be improved.

It can be seen that Examples 1 to 3 have superior irreversible capacity increases and lifetime characteristics due to the volume expansion in the cathode active material, compared to those of Comparative Examples 1 to 3. Accordingly, with respect to Examples 1 to 3, it may be preferred that the particle size distribution of silicon-based primary particles be D10≥50 nm and D90≤150 nm, and that D50 be between 80 nm and 100 nm.

According to an embodiment of the present invention, the silicon-based primary particles may be prepared such that the sphericity, which is defined by Equation 1 below, is in the range of 0.5 to 0.9 or below, and by using the silicon-based primary particles having said sphericity, an irreversible reaction caused by cracks or fractures of the silicon particles during charging can be suppressed or reduced. Those particles which have a sphericity of less than 0.5 may be undifferentiated from the thin edge thereof by a plurality of charging/discharging operations and thereby the lifetime may deteriorate. In contrast, when the sphericity is greater than 0.9, cracks or fractures are easily caused by the tensile stress applied to the lithiated layer. The formation of an SEI layer is promoted in the silicon-based primary particles exposed by the cracks or fractures, resulting in deterioration of the lifetime of the battery.

$\begin{matrix} {{Sphericity} = \frac{2\sqrt{\pi \; A}}{p}} & \left\lbrack {{Equation}\mspace{14mu} 1} \right\rbrack \end{matrix}$

In Equation 1 above, A is a projected area of the two-dimensionally projected silicon-based primary particles, and P is a perimeter of the two-dimensionally projected silicon-based primary particles. The sphericity of the silicon-based primary particles may be measured from the images obtained from a scanning electron microscope using commercially available software such as ImageJ® (e.g. Imagej136). Alternatively, the sphericity may be measured by an FPIA-3000® flow particle image analyzer manufactured by SYSMEX (Kobe, Japan).

According to another embodiment of the present invention, the silicon-based primary particles may include a core of the silicon particle and a silicon oxide layer encompassing the core. The silicon oxide layer may be a natural oxide layer or may include a chemical silicon oxide or thermal oxide that has been artificially grown using an oxygen-containing solvent (i.e., alcohols, distilled water, or peroxide compounds). The silicon particle core may be polysilicon or a single crystal, and may even have a low degree of crystallinity or may be amorphous. Additionally, the silicon-based primary particles may include not only silicon particles having a purity of 99% or greater where capacity maximization is possible, but also any element selected from the group consisting of tin (Sn), antimony, (Sb), zinc (Zn), germanium (Ge), aluminium (Al), copper (Cu), bismuth (Bi), cadmium (Cd), magnesium (Mg), arsenic (As), gallium (Ga), lead (Pb), and iron (Fe), or an intermetallic compound of two or more thereof. In another embodiment, the silicon particle core 100 may have closed pores therein.

In particular, in the silicon-based primary particles, the oxygen content relative to the total weight of the silicon particle cores and the silicon oxide layer may be in the range of 9 wt % to 20 wt %, and preferably 10 wt % to 17 wt %. Within the above range of oxygen content, both the initial charging rate and the capacity retention characteristic are maintained at 80% or higher, with the result that silicon-based primary particles and thus a silicon-based active material particle suitable for commercialization may be provided. When the oxygen content is less than 9 wt %, the effect of suppressing volume expansion is insignificant, and thus the capacity retention of the silicon-based active material complex is reduced to less than 80%, and the lifetime deterioration due to the volume change cannot be improved. However, when the oxygen content exceeds 20 wt %, the capacity retention characteristic is improved, but the initial charging rate may be reduced to less than 80% thereby causing the energy density to deteriorate.

FIG. 3 is a flowchart showing a method of preparing silicon-based primary particles according to an embodiment of the present invention.

With reference to FIG. 3, first silicon powder is provided (S10). The silicon powder is a commercially available granulated particle having an average diameter in the range of a few micrometers to a few thousand micrometers. The silicon powder may be polycrystalline or a single crystal, but the present invention is not limited thereto. A dispersion mixture in which the silicon powder is dispersed in an oxidizing solvent in a liquid state is provided (S20).

In an embodiment, the oxidizing solvent is for forming a chemical oxide layer of silicon and may be water, deionized water, an alcoholic solvent, or a mixture of two or more thereof. The alcoholic solvent may be any solvent selected from the group consisting of ethyl alcohol, methyl alcohol, glycerol, propylene glycol, isopropyl alcohol, isobutyl alcohol, polyvinyl alcohol, cyclohexanol, octyl alcohol, decanol, hexadecanol, ethylene glycol, 1,2-octanediol, 1,2-dodecanediol, and 1,2-hexadecanediol, or a mixture thereof. Preferably, the alcoholic solvent may be ethyl alcohol.

Then, to the silicon powder of the dispersion mixture, the mechanical stress energy (Es) defined by Equation 2 below is applied in the range of 9 m/s to 18 m/s and thereby refined silicon particles are formed (S30). Such a refining process is efficient for the production of silicon particles with narrow particle size distribution, and when the pulverization process is performed by applying the stress energy in the above range, fine silicon particles having a narrow particle size distribution can be produced. The silicon-based active material particles according to the examples of the present invention are controlled so as to have a particle size distribution of D10≥50 nm and D90≤150 nm. Additionally, D100 is controlled so as to be less than 250 nm and D50 is controlled so as to have a range of 80 nm to 100 nm.

$\begin{matrix} {{Es} = \frac{\pi*d*V}{60*\eta}} & \left\lbrack {{Equation}\mspace{14mu} 2} \right\rbrack \end{matrix}$

(In the equation) above, π is a circumferential rate, d is a diameter of a rotor, V is an RPM, and η is a viscosity.

In an embodiment, the application of stress energy to the silicon powder may be performed by a milling method, in which the dispersion mixture and abrasive particles are charged into a cylindrical or conical container rotating about a central axis. The abrasive particles may be beads including ceramic particles, metal particles, or a mixture thereof, but the present invention is not limited thereto. The abrasive particles may apply mechanical compression and shear stress to the silicon powder of the dispersion mixture by having an appropriate average size relative to the size of the silicon powder. In another embodiment, the application of mechanical stress energy to the silicon powder may be carried out by grinding which performs pressing and abrasion while simultaneously supplying the dispersion mixture between a spinning abrasive plate and a fixed plate.

In an embodiment, before the step of drying the resulting product, an aging step may be additionally performed to further relieve the stress by further oxidizing the refined silicon particles, by dispersing and stirring the resulting product into any one of the above-mentioned oxidizing solvents or a mixed solution thereof (S45). Through the aging process, the residual stress of the cores and/or a chemical oxide layer of the silicon particles accumulated during the refining process using the prior stress energy is relieved, and a chemical oxide layer is additionally formed to increase the strength of the chemical oxide layer, and thereby the chemical oxide layer may faithfully serve as a clamping layer to suppress the volume change of the cores of the silicon particles during charging and discharging.

FIG. 3 is a cross-sectional view of an electrode employing silicon-based primary particles according to an embodiment of the present invention.

With reference to FIG. 3, the lithium battery 10 includes an anode 13, a cathode 12, and a separator 14 disposed between the cathode 13 and the anode 12. The anode 13, cathode 12, and a separator 14 are wound or folded and received in a battery container 15. Then, an electrolyte may be injected into the battery container 15 and it may be sealed with an inclusion member 16 and thereby the lithium battery 10 may be completed. The battery container 15 may be cylindrical, square, of thin-film type, etc. The lithium battery may be a lithium ion battery. In particular, the cathode 12 may include the cathode active material described above.

The lithium battery is suitable for applications requiring high capacity, high output, and high-temperature operation (e.g. electric vehicles) in addition to the uses in conventional mobile phones, portable computers, etc., and the lithium battery may also be used in hybrid vehicles, etc. by combining with a conventional internal combustion engine, a fuel cell, a supercapacitor, etc. In addition, the lithium battery may be used for all other applications requiring high output, high voltage, and high-temperature operation.

MODES FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail with respect to specific embodiments, but the present invention is not limited to these embodiments.

Examples

A commercially available polysilicon powder (2 kg) having an average diameter of about 5 μm was dispersed in an oxidizing solvent (10 kg) of 100% ethanol to prepare a dispersion mixture. The bead mill pulverization process in which the stress energy was controlled under the conditions shown in Table 1 was performed to prepare the silicon-based primary particles of the examples and comparative examples, and the sphericity and particle size distribution of the prepared particles are shown in Table 2 below. The purity of the analyzed silicon-based primary particles was greater than 99%. The above preparation method is exemplary and the silicon particles may be prepared by other abrasive processes or by electrochemical explosion of a bulk silicon material (e.g. silicon rods and wafers).

TABLE 1 Stress Rotor Size Viscosity Milling Energy (cm) V (rpm) (P) Time (hr) (m/s) Example 1 12.2 2500 100 17.5 16.0 Example 2 14.4 2500 200 22 9.4 Example 3 17.8 1900 100 17 17.7 Comparative 17.8 2500 100 14 23.3 Example 1 Comparative 5.5 4500 300 33 4.3 Example 2

TABLE 2 D10 D50 D90 Particle Distribution Sphericity (nm) (nm) (nm) Width (D90 − D10)/D50 Example 1 0.8 50 100 150 1.00 Example 2 0.75 55 95 140 0.89 Example 3 0.76 58 88 130 0.82 Comparative 0.5 30 62 105 1.21 Example 1 Comparative 0.4 88 142 257 1.19 Example 2

Referring to Tables 1 and 2, as in Examples 1 to 3, when silicon powder is subjected to wet pulverization under stress energy in the range of about 9 m/s to 18 m/s, it can be seen that the sphericity falls within the range of 0.5 to 0.9, and the particle distribution width is less than 1 in the value range where D10 is 50 or greater and D90 is 150 or less. Meanwhile, in Comparative Examples 1 and 2, it can be seen that the particle distribution is spread over a relatively wide range and the particle distribution width exceeds 1. Additionally, in Comparative Example 1, it can be seen that when the applied stress energy is too strong, the process time is reduced, but the particle size cannot be controlled so that the particle distribution width exceeds 1, whereas in Comparative Example 2, it is shown that when the stress energy is reduced, the desired particle size distribution cannot be obtained even after a considerable milling time.

Table 3 below shows the initial efficiency and proportion of capacity retention of half cells, in which silicon-based primary particles having the sphericity and particle size distribution of Table 2 prepared according to examples and comparative examples were slurried to prepare negative electrodes. The capacity retention results are those evaluated after 50 charging/discharging cycles. The reference initial capacity is 4,200 mAh/g, which is the theoretical capacity of silicon.

TABLE 3 Particle Distri- Weight Retention bution Initial Ratio @ 50 Width Sphericity Efficiency Capacity Times Example 1 1.00 0.8 88% 2455 mAh/g 95% Example 2 0.89 0.75 89% 2387 mAh/g 96% Example 3 0.82 0.76 90% 2410 mAh/g 98% Comparative 1.21 0.6 83% 2040 mAh/g 74% Example 1 Comparative 1.19 0.5 80% 2148 mAh/g 71% Example 2

Referring to Table 3, comparison of Examples 1, 2, and 3 and Comparative Examples 1 and 2 shows that the initial efficiencies were all maintained at levels above 80%, which are levels enabling commercialization, and the capacity to weight ratio was also shown to be 2,000 mAh/g or greater. From the aspect of capacity retention, the initial efficiencies were reduced to less than 75% in the case of particles where the particle distribution width exceeded 1. The initial efficiencies were maintained at levels above 95% in the case of particles where the particle distribution width was less than 1 and the sphericity was in the range of 0.7 to 0.8. The improvement in lifetime characteristics was due to the ability to alleviate the increase of irreversible capacity due to volume expansion in a cathode active material when the particle size distribution of the silicon primary particles used as the cathode active material was prepared so as to be small and uniform within a certain range.

The present invention described above is not limited to exemplary embodiments and accompanying drawings thereof, and it will be apparent to those skilled in the art that various substitutions, modifications, and changes can be made hereto without departing from the technical concept of the present invention defined in the following claims.

<Refernce Explanation> 10: lithium battery 13: anode 12: cathode 14: separator 15: battery container 16: inclusion member 

1. A cathode active material for a secondary battery, wherein the cathode active material comprises silicon-based primary particles and a particle size distribution of the silicon-based primary particles is D10≥50 nm and D90≤150 nm.
 2. The cathode active material for a secondary battery as claimed in claim 1, wherein the sphericity of the silicon-based primary particles is in the range of 0.5 to 0.9.
 3. The cathode active material for a secondary battery as claimed in claim 1, wherein the silicon-based primary particles comprise a silicon particle core and a silicon oxide layer formed on the core.
 4. The cathode active material for a secondary battery as claimed in claim 3, wherein the oxygen content relative to the total weight of the silicon-based primary particles is limited to the range of 9 wt % to 20 wt %.
 5. The cathode active material for a secondary battery as claimed in claim 1, wherein the purity of the silicon-based primary particles is 99% or greater.
 6. The cathode active material for a secondary battery as claimed in claim 1, wherein the particle distribution width of the silicon-based primary particles is 1.0 or less.
 7. A method for preparing a cathode active material for a secondary battery, the method comprising: a step of providing silicon powder; a step of providing a dispersion mixture in which the silicon powder is dispersed in an oxidizing solvent; a step of applying mechanical stress energy (Es), which is defined by the equation below, to the silicon powder of the dispersion mixture to form refined silicon particles in which the particle size distribution is D10≥50 nm and D90≤150 nm; and a step of drying the resulting product comprising the refined silicon particles to obtain silicon-based primary particles: ${Es} = \frac{\pi*d*V}{60*\eta}$ (wherein π is a circumferential rate, d is a diameter of a rotor, V is an RPM, and η is a viscosity).
 8. The method as claimed in claim 7, wherein the step of forming refined silicon particles is a step of forming a chemical oxide layer on the refined silicon particles by means of the oxidizing solvent while simultaneously applying the mechanical stress energy.
 9. The method as claimed in claim 7, wherein the oxidizing solvent comprises water, deionized water, an alcoholic solvent, or a mixture of two or more thereof.
 10. The method as claimed in claim 9, wherein the alcoholic solvent comprises any solvent selected from the group consisting of ethyl alcohol, methyl alcohol, glycerol, propylene glycol, isopropyl alcohol, isobutyl alcohol, polyvinyl alcohol, cyclohexanol, octyl alcohol, decanol, hexadecanol, ethylene glycol, 1,2-octanediol, 1,2-dodecanediol, and 1,2-hexadecanediol, or a mixture thereof.
 11. The method as claimed in claim 7, wherein the step of applying mechanical stress energy is achieved by a mill pulverization process using a composition of abrasive particles along with the oxidizing solvent. 